EP2700394B1 - Use of a solvent-free adhesion promoter to create an adhesive bond between dental composites and the surface of dental frameworks made of high-performance polymers - Google Patents

Use of a solvent-free adhesion promoter to create an adhesive bond between dental composites and the surface of dental frameworks made of high-performance polymers Download PDF

Info

Publication number
EP2700394B1
EP2700394B1 EP13003271.7A EP13003271A EP2700394B1 EP 2700394 B1 EP2700394 B1 EP 2700394B1 EP 13003271 A EP13003271 A EP 13003271A EP 2700394 B1 EP2700394 B1 EP 2700394B1
Authority
EP
European Patent Office
Prior art keywords
adhesive agent
dental
methacrylate
adhesion promoter
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13003271.7A
Other languages
German (de)
French (fr)
Other versions
EP2700394A2 (en
EP2700394A3 (en
Inventor
Klaus Ruppert
Alfred Hohmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kulzer GmbH
Original Assignee
Kulzer GmbH
Kulzer and Co GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kulzer GmbH, Kulzer and Co GmbH filed Critical Kulzer GmbH
Publication of EP2700394A2 publication Critical patent/EP2700394A2/en
Publication of EP2700394A3 publication Critical patent/EP2700394A3/en
Application granted granted Critical
Publication of EP2700394B1 publication Critical patent/EP2700394B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to the promotion of adhesion and the production of an adhesive bond between high-performance polymers and dental composites, in particular with dental veneering composites.
  • prosthetic work such as crowns or bridges require a supporting substructure to ensure mechanical stability.
  • These frameworks typically consist of metal alloys or metal-free materials such as ZrO 2 , Al 2 O 3 or high-performance polymers such as PEEK.
  • ZrO 2 zirconium oxide
  • Al 2 O 3 aluminum oxide
  • PEEK high-performance polymers
  • these are veneered with a dental composite or, in the case of metal frameworks, with a ceramic.
  • An adhesion promoter is typically used to ensure a permanent bond.
  • the surface is mechanically pretreated, usually by sandblasting.
  • an adhesion promoter layer is applied to the sand-blasted framework, which creates a bond between the framework surface and the subsequent (meth) acrylate-based layers.
  • a layer of a relatively transparent, flowable material is then applied to the adhesion promoter, which can also flow into the dead spaces in the undercuts and fill them up. It must be ensured that the material hardens sufficiently there.
  • One or more layers of opaque can then be applied to this flowable layer in order to conceal the framework in color.
  • the actual veneering composite then forms the end of the layer expansion.
  • WO2008 / 113541A2 relates to conditioning agents which are suitable for polymers selected from polyarylates, polyarylene sulfides, polysulfones, liquid crystalline polymers, polyimides, polyetherimides, polyamideimides, polyaryletherketones.
  • the conditioning agents contain an adhesive and a higher-boiling solvent with dipole character, selected from dimethyl sulfoxide, phenol, diphenyl sulfone, cyclohexanone, acetylacetone and ethylene glycol.
  • the application comprises applying the conditioning agent to at least part of the surface of the shaped body, allowing the conditioning agent to act, and optionally applying a curable mixture to the surface of the shaped body conditioned with conditioning agent.
  • the examples relate to DMSO-containing conditioning agents. According to the safety data sheet, DMSO is not harmless and not suitable for use in the mouth (product name dimethyl sulfoxide (DMSO).
  • DE4233886C1 relates to a polymerizable conditioning agent based on methacryl and a method for pretreating the surface of molded bodies made of polyacrylate, polymethacrylate and polycarbonate plastics prior to the application of polymerizable methacrylate material.
  • a method is to be specified by means of which a permanent bond between a high-performance polymer such as e.g. PEEK and a (meth) acrylate-based veneering composite can be produced. Solvents that may be considered problematic should be avoided.
  • the surface of the framework is mechanically pretreated, preferably sandblasted, in order to clean the surface, activate it and create retentive anchors.
  • the abrasive is preferably 110 ⁇ m corundum.
  • a light-curing, low-viscosity or flowable, solvent-free methacrylate-based component (adhesion promoter or conditioning agent), which forms a thin film on the framework surface and, after curing, also leads to a retentive adhesive bond.
  • a light-curing, low-viscosity or flowable, solvent-free methacrylate-based component (adhesion promoter or conditioning agent), which forms a thin film on the framework surface and, after curing, also leads to a retentive adhesive bond.
  • PMMA polymethyl methacrylate
  • MMA methyl methacrylate
  • bifunctional methacrylate-based monomers such as UDMA (urethane dimethacrylate)
  • photoinitiator s
  • agents for adjusting the viscosity can also optionally be present, such as finely divided silicas, which can be silanized in a manner known to the person skilled in the art.
  • the general formulation of such an adhesion promoter is, for example, as follows (in% by weight): 60 to 70% MMA 5 to 15% PMMA 20 to 30% UDMA 0.1 to 5% Photoinitiator, preferably from the group of acylphosphine photoinitiators, 0.05 to 5% Stabilizer, preferably from the group of sterically hindered phenols, such as, for example, 2,6-di-tert-butyl-4-methyl phenol.
  • the polymethyl methacrylate can be used as such in the preparation of the adhesion promoter, preferably in the form of polymer beads with a particle size of 10-150 micrometers, or as a solution (or partial solution) in the methyl methacrylate monomers.
  • a polymethyl methacrylate with an average molecular weight of 120,000-200,000 is preferred.
  • a layer thickness of 0.5 to 2.5 ⁇ m has proven to be advantageous when the adhesion promoter is applied once and from 4.5 to 7.5 ⁇ m when the adhesion promoter is applied twice.
  • the middle of these areas is particularly preferred, that is to say around 1-2 ⁇ m for a single application and around 5 ⁇ m for a double application.
  • a layer thickness of around 10 ⁇ m is achieved
  • the viscosity of the adhesion promoter is preferably in the range of approx. 10-30 mPas at 23 ° C.
  • additives can also be used as means for adjusting the viscosity, e.g. Silicas, of which primarily pyrogenic silicas.
  • the framework e.g. based on PEEK, after treatment with the bonding agent, e.g. veneered with a veneering composite. Examples are Signum® composite or Signum® matrix from Heraeus Kulzer.
  • the curing is preferably carried out by a curing mechanism in the UV or visible spectral range.
  • a curing mechanism in the UV or visible spectral range.
  • the use of new types of IR sensitive initiators is also possible.
  • Another advantage of the method according to the invention is simple processing and the absence of dangerous and / or toxic chemicals (such as in WO2008 / 113541A2 suggested). In addition, the coating does not have to take effect.
  • the usual dental composite mixtures based on monomer mixtures and fillers can be used as dental composites.
  • Suitable monomers are conventional in the dental field, such as monomeric (meth) acrylates such as ethylene glycol dimethacrylate EDMA, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate TEGDMA, glycerol dimethacrylate GDMA, glycerol trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, derivatives of bisphenol A such as bisphenol-A dimethacrylate, and bisphenol -A-diglycol dimethacrylate, urethane methacrylate available from diisocyanates and hydroxyalkyl methacrylates, and reaction products of polyols, diisocyanates and hydroxyalkyl methacrylates according to DE3703080A1 or DE3703120A1 ; C 1-12 ,
  • Suitable fillers are known to the person skilled in the art. Examples are inert and reactive dental glasses such as barium silicate glass, strontium silicate glass, borosilicate glass and fluoroalumosilicate glass or pyrogenic, precipitated or fossil silicas. Mixtures of differently sized filler particles with particle sizes between 0.001 and 100 ⁇ m are preferably used.
  • Micro- and / or nano-scale fillers e.g. Metal, semimetal or mixed metal oxides, silicates, nitrides, sulfates, titanates, zirconates, stannates, tungstates, silicon dioxide or mixtures of these compounds, also spherical fillers, powders, other glasses or glass ceramics and their mixtures, as well as filled or unfilled fragment polymers and / or bead polymers.
  • the fillers can be surface-modified, preferably organically surface-modified such as, for example, silanized.
  • a surface-modified filler can have functional groups on its surface that can react chemically, preferably free-radically, with the monomers or have a high affinity for the polymer matrix formed from the monomers, the filler preferably being surface-modified with a reactive silane containing acrylate or methacrylate groups.
  • the method according to the invention is preferably used to promote adhesion between the framework made of high-performance polymer and the layers of so-called opaquers applied to the adhesion promoter layer (these are strongly white-pigmented composites for laminating the framework colors).
  • opaquers applied to the adhesion promoter layer (these are strongly white-pigmented composites for laminating the framework colors).
  • dental composites can also be applied directly.
  • the method according to the invention is characterized by its simplicity and efficiency: application, exposure, no long waiting for penetration, the next layer (e.g. opaque dental composite) can be applied immediately, and a solid and permanent bond results.
  • the next layer e.g. opaque dental composite
  • PEEK polyetheretherketone
  • PEKK polyetherketoneketone
  • POM polyoxymethylene
  • Polyamides such as e.g. the Zellamid® types described in detail in the examples.
  • the adhesion promoter is applied twice to the framework material and exposed with the Heraflash® laboratory light lamp (Heraeus Kulzer) for 90 seconds. Then 2 layers of Signum® opaque F (Heraeus Kulzer) are applied and each cured for 90 seconds with Heraflash®.
  • the finish is a layer of Signum® composite (Heraeus Kulzer), possibly in different colors, which is cured for 90 seconds and then finally cured for another 180 seconds for tempering.
  • Test specimens produced with this procedure give the following measured values for testing the shear bond strength according to ISO 10477 (Table A): Framework material Vestkeep / Evonik Adhesion promoter x x 1x Signum opaque F x 2x 2x Signum composite YES TWL (5 ° C / 55 ° C) 5000 Shear bond bond [MPa] 2.6 14.5 18.5
  • a shear bond of at least 5 MPa must be achieved when working without macromechanical retention.
  • the test specimens are subjected to a temperature change load of 5000 cycles before shearing.
  • the adhesion promoter according to the invention is also suitable for other high-performance polymers besides PEEK. This can be seen from the following table B: It can be seen that the adhesive bond with different polymers is very clearly above the norm and is therefore more than sufficient: Framework material Cell amide 202 (PAG) Cell amide 900 (POM) Cell amide 202 XN Bioloren Adhesion promoter 2x 2x 2x 2x Signum opaque F 2x 2x 2x 2x Signum composite YES YES YES TWL (5 ° C / 55 ° C) 5000 5000 5000 5000 5000 Shear bond bond [MPa] 19.5 18.6 18.5 22.8
  • POM-C is a semi-crystalline thermoplastic, made from acetal copolymer granules, and is characterized by a low coefficient of friction and good wear resistance. Since the water absorption is very low, the dimensional stability is much better than with polyamides. POM is resistant to many chemicals and solvents. POM offers high strength and rigidity with easy machinability.
  • ZELLAMID® 900 is also known for its high mechanical strength, heat resistance and good sliding properties.
  • ZELLAMID® 900 is free of medium porosity according to ASTM D-61 00 and most qualities are approved for food contact (BfR, FDA).
  • POM-C is more resistant to hot water than POM-H (homopolymer).
  • ZELLAMID® 202 (Zell-Metall Ges.mbH. Engineering Plastics, Kaprun - Austria): ZELLAMID® 202 is a tough material with high abrasion and impact resistance based on polyamide 6 (PA 6). PA 6 is often used as a substitute for bronze, aluminum and other non-ferrous metals because it offers significant weight advantages.
  • ZELLAMID® 202 has a specific weight of 1.15 g / cm 3 and bronze 8.8 g / cm 3 , which results in a very attractive price-performance ratio. If ZELLAMID® 202 is used with sliding friction, lubrication can be reduced and the abrasion of the metal counter surface is reduced. Therefore, overall very good mechanical properties are offered.
  • PA 6 can absorb up to 8% water (by weight) in a damp environment or in water. This additionally increases the excellent impact and fatigue strength (also with vibrations), but can also lead to dimensional changes. Mechanical and electrical properties, as well as dimensional stability, are also influenced by moisture.
  • ZELLAMID® 202 is approved for food contact (BfR, FDA).
  • ZELLAMID® 202 XN Zell-Metall Ges.mbH. Engineering Plastics, Kaprun - Austria: This polyamide is a high-tech material that was developed by Zell-Metall Engineering Plastics using the latest technologies (nanotechnology). This one unique Reinforced PA 6 outperforms normal PA 6, PA 6.6 and also some properties of PA 6.6 with 30% glass fibers.
  • ZELLAMID® 202 XN has an increased continuous use temperature of 140 ° C with a HDT of 168 ° C. Increased mechanical strength with a modulus of elasticity of 4200 MPa (ISO 527, dry) as well as reduced water absorption, which ensure improved dimensional stability, are further properties to be emphasized.
  • This product is approved for food contact (BfR, FDA) and, compared to glass-filled polyamides, offers a specific weight that is approx. 15% lower, which results in reduced volume costs.
  • the flame-retardant effect of the nanoparticles improves the fire behavior.
  • ZELLAMID 202 XN is the alternative for many applications in which other products do not have the necessary properties (e.g. increased service temperature), as standard materials are often too soft, e.g. PTFE or too expensive like PEEK. Compared to glass-filled polyamides, this material is easier to machine because no preheating or the use of diamond tools is necessary.
  • VESTAKEEP® PEEK grades for medical technology (Evonik Industries AG, Essen, Germany): The products VESTAKEEP® M2G, VESTAKEEP® 12G, VESTAKEEP® M4G, VESTAKEEP® 14G, and the powder VESTAKEEP® M4P are available for applications in medical technology. The formulation of these products is tailored to a high level of biocompatibility and an "in vitro" batch test for cytotoxicity according to EN ISO 10993-5 offers additional security.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Dental Preparations (AREA)

Description

Die Erfindung betrifft die Haftvermittlung und die Herstellung eines Haftverbundes zwischen Hochleistungspolymeren und Dentalkompositen, insbesondere mit dentalen Verblendkompositen.The invention relates to the promotion of adhesion and the production of an adhesive bond between high-performance polymers and dental composites, in particular with dental veneering composites.

Technischer Hintergrund:Technical background:

Prothetische Arbeiten wie z.B. Kronen oder Brücken erfordern in vielen Fällen zur Gewährleistung der mechanischen Stabilität eine tragende Unterkonstruktion. Typischerweise bestehen diese Gerüste aus Metalllegierungen oder aus metallfreien Werkstoffen wie z.B. ZrO2, Al2O3 oder Hochleistungspolymeren wie PEEK. Um der Zahnrestauration auf derartigen Gerüstkonstruktionen ein ästhetisches Aussehen zu verleihen, werden diese mit einem Dental-Komposit oder im Fall von Metallgerüsten einer Keramik zahnfarben verblendet. Zur Gewährleistung eines dauerhaften Verbunds wird typischerweise ein Haftvermittler verwendet.In many cases, prosthetic work such as crowns or bridges require a supporting substructure to ensure mechanical stability. These frameworks typically consist of metal alloys or metal-free materials such as ZrO 2 , Al 2 O 3 or high-performance polymers such as PEEK. In order to give the tooth restoration an aesthetic appearance on framework structures of this type, these are veneered with a dental composite or, in the case of metal frameworks, with a ceramic. An adhesion promoter is typically used to ensure a permanent bond.

Zunächst wird die Oberfläche mechanisch vorbehandelt, in der Regel durch Sandstrahlen. Auf das sandgestrahlte Gerüst wird zunächst eine Haftvermittlerschicht aufgebracht, welche einen Verbund zwischen der Gerüstoberfläche und den nachfolgenden (Meth)acrylat-basierten Schichten herstellt. Auf den Haftvermittler wird anschließend eine Schicht eines relativ transparenten, fließfähigen Materials aufgebracht, welches auch in die Toträume in den Hinterschneidungen einfließen und diese auffüllen kann. Dabei muss sichergestellt sein, dass das Material dort ausreichend aushärtet. Auf diese fließfähige Schicht können anschließend eine oder mehrere Schichten Opaker aufgebracht werden, um das Gerüst farblich zu kaschieren. Den Abschluss des Schichtausbaus bildet dann das eigentliche Verblendkomposit.First, the surface is mechanically pretreated, usually by sandblasting. First, an adhesion promoter layer is applied to the sand-blasted framework, which creates a bond between the framework surface and the subsequent (meth) acrylate-based layers. A layer of a relatively transparent, flowable material is then applied to the adhesion promoter, which can also flow into the dead spaces in the undercuts and fill them up. It must be ensured that the material hardens sufficiently there. One or more layers of opaque can then be applied to this flowable layer in order to conceal the framework in color. The actual veneering composite then forms the end of the layer expansion.

Stand der TechnikState of the art

WO2008/113541A2 betrifft Konditionierungsmittel, die für Polymere ausgewählt aus Polyarylaten, Polyarylensulfiden, Polysulfonen, flüssigkristallinem Polymer, Polyimiden, Polyetherimiden, Polyamidimiden, Polyaryletherketonen, geeignet sind. Die Konditionierungsmittel enthalten ein Haftmittel und ein höhersiedendes Lösemittel mit Dipolcharakter, ausgewählt aus Dimethylsulfoxid, Phenol, Diphenylsulfon, Cylohexanon, Acetylaceton und Ethylenglykol. Die Anwendung umfasst Auftragen des Konditionierungsmittels auf zumindest einen Teil der Oberfläche des Formkörpers, Einwirkenlassen des Konditionierungsmittels, und optional Auftragen einer härtbaren Mischung auf die mit Konditionierungsmittel konditionierte Oberfläche des Formkörpers. Die Beispiele betreffen DMSO-haltige Konditionierungsmittel. DMSO ist gemäß Sicherheitsdatenblatt nicht unbedenklich und nicht für die Anwendung im Mund geeignet (Produktname Dimethylsulfoxide (DMSO). WO2008 / 113541A2 relates to conditioning agents which are suitable for polymers selected from polyarylates, polyarylene sulfides, polysulfones, liquid crystalline polymers, polyimides, polyetherimides, polyamideimides, polyaryletherketones. The conditioning agents contain an adhesive and a higher-boiling solvent with dipole character, selected from dimethyl sulfoxide, phenol, diphenyl sulfone, cyclohexanone, acetylacetone and ethylene glycol. The application comprises applying the conditioning agent to at least part of the surface of the shaped body, allowing the conditioning agent to act, and optionally applying a curable mixture to the surface of the shaped body conditioned with conditioning agent. The examples relate to DMSO-containing conditioning agents. According to the safety data sheet, DMSO is not harmless and not suitable for use in the mouth (product name dimethyl sulfoxide (DMSO).

DE4233886C1 betrifft ein polymerisierbares Konditionierungsmittel auf Methacryl-Basis und ein Verfahren zur Vorbehandlung der Oberfläche von Formkörpern aus Polyacrylat-, Polymethacrylat- und Polycarbonat-Kunststoffen vor dem Auftragen von polymerisierbarem Methacrylat-Material. DE4233886C1 relates to a polymerizable conditioning agent based on methacryl and a method for pretreating the surface of molded bodies made of polyacrylate, polymethacrylate and polycarbonate plastics prior to the application of polymerizable methacrylate material.

Aufgabenstellung:Task:

Es ist ein Verfahren anzugeben, mit dem ein dauerhafter Verbund zwischen einem Hochleistungspolymer wie z.B. PEEK und einem (meth-)acrylatbasierten Verblendkomposit hergestellt werden kann. Eventuell als problematisch angesehene Lösungsmittel sollten vermieden werden.A method is to be specified by means of which a permanent bond between a high-performance polymer such as e.g. PEEK and a (meth) acrylate-based veneering composite can be produced. Solvents that may be considered problematic should be avoided.

Erfindung:Invention:

Die Aufgabe wird durch ein Verfahren nach Anspruch 1 gelöst. Vorteilhafte Ausgestaltungen sind den weiteren Ansprüchen zu entnehmen.The object is achieved by a method according to claim 1. Advantageous configurations can be found in the further claims.

Insbesondere wird die Oberfläche des Gerüstes mechanisch vorbehandelt, vorzugsweise sandgestrahlt, um die Oberfläche zu reinigen, zu aktivieren und retentive Verankerungen zu schaffen. Das Strahlmittel ist bevorzugt 110 µm Korund.In particular, the surface of the framework is mechanically pretreated, preferably sandblasted, in order to clean the surface, activate it and create retentive anchors. The abrasive is preferably 110 μm corundum.

Anschließend erfolgt der Auftrag einer lichthärtenden, gering viskosen oder fließfähigen, lösemittelfreien Methacrylat-basierten Komponente (Haftvermittler bzw. Konditionierungsmittel), welche einen dünnen Film auf der Gerüstoberfläche bildet und nach Härtung zusätzlich zu einem retentiven Haftverbund führt. Sie enthält, PMMA (Polymethylmethacrylat), MMA (Methylmethacrylat), bifunktionelle Methacrylat-basierte Monomere wie z.B. UDMA (Urethandimethacrylat), und Photoinitiator(en) sowie optional Stabilisatoren und anorganische Pigmente. Ferner können ebenfalls optional Mittel zur Einstellung der Viskosität vorhanden sein, wie etwa feinteilige Kieselsäuren, die in dem Fachmann bekannter Weise silanisiert sein können.This is followed by the application of a light-curing, low-viscosity or flowable, solvent-free methacrylate-based component (adhesion promoter or conditioning agent), which forms a thin film on the framework surface and, after curing, also leads to a retentive adhesive bond. It contains PMMA (polymethyl methacrylate), MMA (methyl methacrylate), bifunctional methacrylate-based monomers such as UDMA (urethane dimethacrylate), and photoinitiator (s) as well as optionally stabilizers and inorganic pigments. Furthermore, agents for adjusting the viscosity can also optionally be present, such as finely divided silicas, which can be silanized in a manner known to the person skilled in the art.

Die allgemeine Rezeptur eines derartigen Haftvermittlers ist beispielsweise wie folgt (in Gew.%): 60 bis 70 % MMA 5 bis 15% PMMA 20 bis 30 % UDMA 0,1 bis 5 % Photoinitiator, vorzugsweise aus der Gruppe der Acylphosphin-Photoinitiatoren, 0,05 bis 5 % Stabilisator, bevorzugt aus der Gruppe der sterisch gehinderten Phenole, wie z.B. 2,6-ditert.-butyl-4-methyl phenol. The general formulation of such an adhesion promoter is, for example, as follows (in% by weight): 60 to 70% MMA 5 to 15% PMMA 20 to 30% UDMA 0.1 to 5% Photoinitiator, preferably from the group of acylphosphine photoinitiators, 0.05 to 5% Stabilizer, preferably from the group of sterically hindered phenols, such as, for example, 2,6-di-tert-butyl-4-methyl phenol.

Das Polymethylmethacrylat kann bei der Zubereitung des Haftvermittlers als solches, vorzugsweise in Form von Polymerisat-Perlen mit einer Teilchengröße von 10-150 Mikrometer, oder als Lösung (oder teilweise Lösung) in den Methylmethacrylat-Monomeren, eingesetzt werden. Ein Polymethylmethacrylat mit einem mittleren Molekulargewicht von 120 000 - 200 000 wird dabei bevorzugt.The polymethyl methacrylate can be used as such in the preparation of the adhesion promoter, preferably in the form of polymer beads with a particle size of 10-150 micrometers, or as a solution (or partial solution) in the methyl methacrylate monomers. A polymethyl methacrylate with an average molecular weight of 120,000-200,000 is preferred.

Bei der aufgebrachten Haftschicht hat sich eine Schichtdicke von 0,5 bis 2,5 µm bei einfachem Auftragen und von 4,5 bis 7,5 µm bei zweifachem Auftragen des Haftvermittlers als vorteilhaft erwiesen. Die Mitte dieser Bereiche ist besonders bevorzugt, also um 1-2 µm bei einfachem Auftragen und um 5 µm bei zweifachem Auftragen. Bei dreifachem Auftragen werden Schichtdicken um 10 µm erreichtFor the applied adhesive layer, a layer thickness of 0.5 to 2.5 μm has proven to be advantageous when the adhesion promoter is applied once and from 4.5 to 7.5 μm when the adhesion promoter is applied twice. The middle of these areas is particularly preferred, that is to say around 1-2 µm for a single application and around 5 µm for a double application. When applied three times, a layer thickness of around 10 µm is achieved

Die Viskosität des Haftvermittlers liegt vorzugsweise im Bereich von ca. 10 - 30 mPa·s bei 23 °C. Als Mittel zur Einstellung der Viskosität kommen neben der Wahl der eingesetzten Monomere, Oligomere und Polymere auch Zusatzstoffe in Frage, z.B. Kieselsäuren, davon in erster Linie pyrogene Kieselsäuren. Das Gerüst, z.B. auf PEEK-Basis, kann nach Behandlung mit dem Haftvermittler z.B. mit einem Verblendkomposit verblendet werden. Beispiele sind Signum® composite oder Signum® matrix der Firma Heraeus Kulzer.The viscosity of the adhesion promoter is preferably in the range of approx. 10-30 mPas at 23 ° C. In addition to the choice of the monomers, oligomers and polymers used, additives can also be used as means for adjusting the viscosity, e.g. Silicas, of which primarily pyrogenic silicas. The framework, e.g. based on PEEK, after treatment with the bonding agent, e.g. veneered with a veneering composite. Examples are Signum® composite or Signum® matrix from Heraeus Kulzer.

Die Aushärtung erfolgt bevorzugt durch einen Härtemechanismus im UV oder sichtbaren Spektralbereich. Auch der Einsatz neuartiger IR sensitiver Initiatoren ist möglich.The curing is preferably carried out by a curing mechanism in the UV or visible spectral range. The use of new types of IR sensitive initiators is also possible.

Weiterer Vorteil des erfindungsgemäßen Verfahrens ist eine einfache Verarbeitung und der Verzicht auf gefährliche und/oder toxische Chemikalien (wie z. B. in WO2008/113541A2 vorgeschlagen). Außerdem ist keine Einwirkzeit der Beschichtung notwendig.Another advantage of the method according to the invention is simple processing and the absence of dangerous and / or toxic chemicals (such as in WO2008 / 113541A2 suggested). In addition, the coating does not have to take effect.

Als Dentalkomposite kommen die üblichen Dental-Kompositmischungen auf der Basis von Monomermischungen und Füllstoffen in Frage.The usual dental composite mixtures based on monomer mixtures and fillers can be used as dental composites.

Beispiele geeigneter Monomere sind die im Dentalbereich üblichen, wie z.B. monomere (Meth)acrylate wie Ethylenglycoldimethacrylat EDMA, Diethylenglycoldimethacrylat, Triethylenglycoldimethacrylat TEGDMA, Glyceroldimethacrylat GDMA, Glyceroltrimethacrylat, Trimethylolpropantrimethacrylat, Pentaerythritoldimethacrylat, Pentaerythritoltrimethacrylat, Pentaerythritoltetramethacrylat, Derivate von Bisphenol A wie Bisphenol-A-dimethacrylat und Bisphenol-A-diglycoldimethacrylat, Urethanmethacrylat erhältlich aus Diisocyanaten und Hydroxyalkylmethacrylaten, sowie Reaktionsprodukte von Polyolen, Diisocyanaten und Hydroxyalkylmethacrylaten gemäß DE3703080A1 oder DE3703120A1 ; C1-12-, vorzugsweise C1-4-Alkylmethacrylate wie Methylmethacrylat, Ethylmethacrylat, n-Propylmethacrylat, Isopropylmethacrylat, n-Butylmethacrylat and t-Butylmethacrylat, Hydroxyalkyl-C1-4-methacrylate wie 2-Hydroxyethylmethacrylat, 2-Hydroxypropylmethacrylat, Diethylenglycolmonomethacrylat, Triethylenglycolmonomethacrylat, Alkoxy-C1-4 alkylmethacrylate wie 2-Methoxyethylmethacrylat, 3-Methoxybutylmethacrylat und Ethyltriglycolmethacrylat. Geeignete Monomere sind davon jeweils die Monomere selbst, daraus hergestellte polymerisierbare Präpolymere sowie Mischungen von diesen.Examples of suitable monomers are conventional in the dental field, such as monomeric (meth) acrylates such as ethylene glycol dimethacrylate EDMA, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate TEGDMA, glycerol dimethacrylate GDMA, glycerol trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, derivatives of bisphenol A such as bisphenol-A dimethacrylate, and bisphenol -A-diglycol dimethacrylate, urethane methacrylate available from diisocyanates and hydroxyalkyl methacrylates, and reaction products of polyols, diisocyanates and hydroxyalkyl methacrylates according to DE3703080A1 or DE3703120A1 ; C 1-12 , preferably C 1-4 alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and t-butyl methacrylate, hydroxyalkyl C 1-4 methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, diethylene glycol , Triethylene glycol monomethacrylate, alkoxy C 1-4 alkyl methacrylates such as 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate and ethyl triglycol methacrylate. Suitable monomers of these are in each case the monomers themselves, polymerizable prepolymers produced therefrom, and mixtures of these.

Geeignete Füllstoffe sind dem Fachmann bekannt. Beispiele sind inerte und reaktive Dentalgläser wie Bariumsilikatglas, Strontiumsilikatglas, Borosilikatglas und Fluoralumosilikatglas oder pyrogene, gefällte oder fossile Kieselsäuren. Bevorzugt werden Mischungen verschieden großer Füllstoffpartikel mit Teilchengrößen zwischen 0,001 und 100 µm eingesetzt.Suitable fillers are known to the person skilled in the art. Examples are inert and reactive dental glasses such as barium silicate glass, strontium silicate glass, borosilicate glass and fluoroalumosilicate glass or pyrogenic, precipitated or fossil silicas. Mixtures of differently sized filler particles with particle sizes between 0.001 and 100 μm are preferably used.

Weiter sind geeignet mikro- und/oder nanoskalige Füllstoffe, z.B. Metall-, Halbmetall- oder Mischmetalloxide, Silikate, Nitride, Sulfate, Titanate, Zirkonate, Stannate, Wolframate, Siliciumdioxid oder Mischungen aus diesen Verbindungen, ferner sphärische Füllstoffe, Pulver weiterer Gläser oder Glaskeramiken und deren Mischungen, sowie außerdem gefüllte oder ungefüllte Splitterpolymerisate und/oder Perlpolymerisate.Micro- and / or nano-scale fillers, e.g. Metal, semimetal or mixed metal oxides, silicates, nitrides, sulfates, titanates, zirconates, stannates, tungstates, silicon dioxide or mixtures of these compounds, also spherical fillers, powders, other glasses or glass ceramics and their mixtures, as well as filled or unfilled fragment polymers and / or bead polymers.

Die Füllstoffe können oberflächenmodifiziert, vorzugsweise organisch oberflächenmodifiziert wie beispielsweise silanisiert sein. Ein oberflächenmodifizierter Füllstoff kann auf seiner Oberfläche funktionelle Gruppen besitzen, die mit den Monomeren chemisch, vorzugsweise radikalisch, reagieren können oder eine hohe Affinität zu der aus den Monomeren gebildeten Polymermatrix haben, wobei der Füllstoff vorzugsweise mit reaktive Acrylat- oder Methacrylatgruppen tragendem Silan oberflächenmodifiziert ist.The fillers can be surface-modified, preferably organically surface-modified such as, for example, silanized. A surface-modified filler can have functional groups on its surface that can react chemically, preferably free-radically, with the monomers or have a high affinity for the polymer matrix formed from the monomers, the filler preferably being surface-modified with a reactive silane containing acrylate or methacrylate groups.

Das erfindungsgemäße Verfahren dient vorzugsweise der Haftvermittlung zwischen dem Gerüst aus Hochleistungspolymer und den auf die Haftvermittlerschicht aufgebrachten Schichten sogenannter Opaker (das sind stark weißpigmentierte Composite zum Kaschieren der Gerüstfarben). Es können aber auch direkt Dentalkomposite aufgetragen werden.The method according to the invention is preferably used to promote adhesion between the framework made of high-performance polymer and the layers of so-called opaquers applied to the adhesion promoter layer (these are strongly white-pigmented composites for laminating the framework colors). However, dental composites can also be applied directly.

Das Verfahren nach der Erfindung zeichnet sich durch seine Einfachheit und Effizienz aus: Auftragen, Belichten, kein langes Warten auf Eindringen, die nächste Schicht (z.B. Opaker Dental-komposit) kann sofort aufgetragen werden, und es ergibt sich ein fester und dauerhafter Verbund.The method according to the invention is characterized by its simplicity and efficiency: application, exposure, no long waiting for penetration, the next layer (e.g. opaque dental composite) can be applied immediately, and a solid and permanent bond results.

Als Hochleistungspolymere kommen in Frage: Polyetheretherketon (PEEK), Polyetherketonketon (PEKK), Polyoxymethylen (POM), sowie Polyamide wie z.B. die in den Beispielen eingehend beschriebenen Zellamid® Typen.The following high-performance polymers can be used: polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyoxymethylene (POM), and polyamides such as e.g. the Zellamid® types described in detail in the examples.

Die folgenden Beispiele zeigen, dass die Haftwerte am besten sind, wenn zweimal mit dem Haftvermittler nach der obigen allgemeinen Rezeptur behandelt wird. Ein dreimaliges oder öfteres Aufbringen ist ebenfalls möglich. Die Beispiele dienen der näheren Erläuterung der Erfindung. Teile- und Prozentangaben beziehen sich wie in der übrigen Beschreibung auf das Gewicht, sofern nicht anders angegeben.The following examples show that the adhesion values are best when treated twice with the adhesion promoter according to the general recipe above. It can also be applied three times or more. The examples serve to explain the invention in more detail. As in the remainder of the description, parts and percentages relate to weight, unless stated otherwise.

Ausführungsbeispiele:Embodiments:

Auf den Gerüstwerkstoff wird nach dem Sandstrahlen mit 110 µm Korund und dem Abspülen mit voll entsalztem Wasser und dem Trocknen mit ölfreier Luft der Haftvermittler 2 x aufgetragen und mit der Laborlichtlampe Heraflash® (Fa. Heraeus Kulzer) für 90 sec. belichtet. Anschließend werden 2 Schichten Signum® opaque F (Fa. Heraeus Kulzer) aufgetragen und jeweils für 90 sec. mit Heraflash® ausgehärtet. Den Abschluss bildet eine Schicht aus Signum® composite (Fa. Heraeus Kulzer), evtl. in verschiedenen Farben, die mit 90 sec. zwischengehärtet und anschließend zur Vergütung nochmals 180 sec. endgehärtet werden.After sandblasting with 110 μm corundum and rinsing with demineralized water and drying with oil-free air, the adhesion promoter is applied twice to the framework material and exposed with the Heraflash® laboratory light lamp (Heraeus Kulzer) for 90 seconds. Then 2 layers of Signum® opaque F (Heraeus Kulzer) are applied and each cured for 90 seconds with Heraflash®. The finish is a layer of Signum® composite (Heraeus Kulzer), possibly in different colors, which is cured for 90 seconds and then finally cured for another 180 seconds for tempering.

Mit diesem Vorgehen hergestellte Prüfkörper ergeben folgende Messwerte für die Prüfung des Scherhaftverbundes nach ISO 10477 (Tabelle A): Gerüstwerkstoff Vestkeep / Evonik Haftvermittler x x 1x Signum opaque F x 2x 2x Signum composite JA TWL (5 °C/55 °C) 5000 Scherhaftverbund [MPa] 2,6 14,5 18,5 Test specimens produced with this procedure give the following measured values for testing the shear bond strength according to ISO 10477 (Table A): Framework material Vestkeep / Evonik Adhesion promoter x x 1x Signum opaque F x 2x 2x Signum composite YES TWL (5 ° C / 55 ° C) 5000 Shear bond bond [MPa] 2.6 14.5 18.5

Nach ISO 10477 muss ein Scherhaftverbund von mind. 5 MPa erreicht werden, wenn man ohne makromechanische Retentionen arbeitet. Nach ISO 10477 werden die Prüfkörper vor dem Abscheren zuvor einer Temperaturwechsellast von 5000 Zyklen unterzogen.According to ISO 10477, a shear bond of at least 5 MPa must be achieved when working without macromechanical retention. According to ISO 10477, the test specimens are subjected to a temperature change load of 5000 cycles before shearing.

Überraschenderweise kommt es zu einer mehr als zufriedenstellenden Haftung mit dem erfindungsgemäßen Haftvermittler, die deutlich über den Normerfordernissen liegt.Surprisingly, there is a more than satisfactory adhesion with the adhesion promoter according to the invention, which is clearly above the standard requirements.

Der erfindungsgemäße Haftvermittler ist auch für andere Hochleistungspolymere außer PEEK geeignet. Dies ist der folgenden Tabelle B zu entnehmen: Es zeigt sich, dass der Haftverbund bei unterschiedlichen Polymeren sehr deutlich über der Norm liegt und damit mehr als ausreichend ist: Gerüstwerkstoff Zellamid 202 (PAG) Zellamid 900 (POM) Zellamid 202 XN Bioloren Haftvermittler 2x 2x 2x 2x Signum opaque F 2x 2x 2x 2x Signum composite JA JA JA JA TWL (5 °C/55 °C) 5000 5000 5000 5000 Scherhaftverbund [MPa] 19,5 18,6 18,5 22,8 The adhesion promoter according to the invention is also suitable for other high-performance polymers besides PEEK. This can be seen from the following table B: It can be seen that the adhesive bond with different polymers is very clearly above the norm and is therefore more than sufficient: Framework material Cell amide 202 (PAG) Cell amide 900 (POM) Cell amide 202 XN Bioloren Adhesion promoter 2x 2x 2x 2x Signum opaque F 2x 2x 2x 2x Signum composite YES YES YES YES TWL (5 ° C / 55 ° C) 5000 5000 5000 5000 Shear bond bond [MPa] 19.5 18.6 18.5 22.8

Diese Werte sind denen des Standes der Technik WO2008/113541A2 um bis zu 46 % überlegen (dort 15,2 MPa für Dentanium, ein Verbundwerkstoff auf PEEK Basis).These values are those of the prior art WO2008 / 113541A2 superior by up to 46% (there 15.2 MPa for Dentanium, a composite material based on PEEK).

Die einzelnen Hochleistungspolymere in der vorstehenden Tabelle sind kommerziell erhältlich und nach Herstellerangaben wie folgt zu beschreiben:
Zellamid® 900/POM-C (Fa. Zell-Metall Ges.mbH. Engineering Plastics, Kaprun - Austria)The individual high-performance polymers in the table above are commercially available and can be described as follows according to the manufacturer's instructions:
Zellamid® 900 / POM-C (Zell-Metall Ges.mbH. Engineering Plastics, Kaprun - Austria)

POM-C ist ein semikristalliner Thermoplast, hergestellt aus Acetalcopolymerisatgranulaten, und zeichnet sich durch einen niederen Reibbeiwert und gute Verschleißfestigkeit aus. Da die Wasseraufnahme sehr gering ist, ist die Dimensionsstabilität viel besser als bei Polyamiden. POM ist gegen viele Chemikalien und auch Lösungsmittel beständig. POM bietet hohe Festigkeit und Steifigkeit bei einfacher Bearbeitbarkeit.POM-C is a semi-crystalline thermoplastic, made from acetal copolymer granules, and is characterized by a low coefficient of friction and good wear resistance. Since the water absorption is very low, the dimensional stability is much better than with polyamides. POM is resistant to many chemicals and solvents. POM offers high strength and rigidity with easy machinability.

ZELLAMID® 900 ist auch bekannt für seine hohe mechanische Festigkeit, Hitzebeständigkeit und guten Gleiteigenschaften. ZELLAMID® 900 ist nach ASTM D-61 00 frei von Mittelporosität und die meisten Qualitäten sind für den Lebensmittelkontakt zugelassen (BfR, FDA). Gut geeignet für Teile, die in feuchter oder nasser Umgebung eingesetzt werden. POM-C ist besser gegen heißes Wasser beständig als POM-H (Homopolymer).ZELLAMID® 900 is also known for its high mechanical strength, heat resistance and good sliding properties. ZELLAMID® 900 is free of medium porosity according to ASTM D-61 00 and most qualities are approved for food contact (BfR, FDA). Well suited for parts that are used in damp or wet environments. POM-C is more resistant to hot water than POM-H (homopolymer).

ZELLAMID® 202(Fa. Zell-Metall Ges.mbH. Engineering Plastics, Kaprun - Austria):
ZELLAMID® 202 ist ein zähes Material mit hoher Abrieb- und Schlagfestigkeit auf der Basis von Polyamid 6 (PA 6). PA 6 wird oft als Ersatzmaterial für Bronze, Aluminium und andere Nichteisenmetalle verwendet, da es erhebliche Gewichtsvorteile bietet. So hat ZELLAMID® 202 ein spezifisches Gewicht von 1,15 g/cm3 und Bronze 8,8 g/cm3, welches ein sehr attraktives Preis-Leistungs-Verhältnis ergibt. Bei Gleitanwendung von ZELLAMID® 202 kann die Schmierung verringert werden und der Abrieb der Metallgegenfläche wird reduziert. Daher werden insgesamt sehr gute mechanische Eigenschaften geboten. PA 6 kann bis zu 8 % Wasser (gewichtsmäßig) in feuchter Umgebung oder in Wasser aufnehmen. Das erhöht die hervorragende Schlag- und Dauerbruchfestigkeit (auch bei Vibrationen) zusätzlich, kann aber auch zu Dimensionsveränderungen führen. Mechanische, elektrische Eigenschaften, wie auch die Dimensionsstabilität werden auch durch die Feuchtigkeit beeinflusst. ZELLAMID® 202 ist für den Lebensmittelkontakt zugelassen (BfR, FDA).ZELLAMID® 202 (Zell-Metall Ges.mbH. Engineering Plastics, Kaprun - Austria):
ZELLAMID® 202 is a tough material with high abrasion and impact resistance based on polyamide 6 (PA 6). PA 6 is often used as a substitute for bronze, aluminum and other non-ferrous metals because it offers significant weight advantages. ZELLAMID® 202 has a specific weight of 1.15 g / cm 3 and bronze 8.8 g / cm 3 , which results in a very attractive price-performance ratio. If ZELLAMID® 202 is used with sliding friction, lubrication can be reduced and the abrasion of the metal counter surface is reduced. Therefore, overall very good mechanical properties are offered. PA 6 can absorb up to 8% water (by weight) in a damp environment or in water. This additionally increases the excellent impact and fatigue strength (also with vibrations), but can also lead to dimensional changes. Mechanical and electrical properties, as well as dimensional stability, are also influenced by moisture. ZELLAMID® 202 is approved for food contact (BfR, FDA).

ZELLAMID® 202 XN (Fa. Zell-Metall Ges.mbH. Engineering Plastics, Kaprun - Austria):
Dieses Polyamid ist ein hochtechnologisches Material, das von Zell-Metall Engineering Plastics unter verwendungsneuester Technologien (Nanotechnologie) entwickelt wurde. Dieses einzigartig verstärkte PA 6 übertrifft leistungsmäßig normales PA 6, PA 6.6 und auch einige Eigenschaften von PA 6.6 mit 30 % Glasfasern. ZELLAMID® 202 XN hat eine erhöhte Dauergebrauchstemperatur von 140 °C mit einer HDT von 168 °C. Erhöhte mechanische Festigkeit mit einem E-Modul von 4200 MPa (ISO 527, trocken) sowie verringerte Wasseraufnahme, welche eine verbesserte Dimensionsstabilität sicherstellen, sind weitere hervorzuhebende Eigenschaften. Dieses Produkt ist für den Nahrungsmittelkontakt (BfR, FDA) zugelassen und bietet im Vergleich zu glasgefüllten Polyamiden ein um ca. 15 % geringeres spezifisches Gewicht, was reduzierte Volumenkosten ergibt. Der flammhemmende Effekt der Nanopartikel bringt eine Verbesserung des Brandverhaltens.ZELLAMID® 202 XN (Zell-Metall Ges.mbH. Engineering Plastics, Kaprun - Austria):
This polyamide is a high-tech material that was developed by Zell-Metall Engineering Plastics using the latest technologies (nanotechnology). This one unique Reinforced PA 6 outperforms normal PA 6, PA 6.6 and also some properties of PA 6.6 with 30% glass fibers. ZELLAMID® 202 XN has an increased continuous use temperature of 140 ° C with a HDT of 168 ° C. Increased mechanical strength with a modulus of elasticity of 4200 MPa (ISO 527, dry) as well as reduced water absorption, which ensure improved dimensional stability, are further properties to be emphasized. This product is approved for food contact (BfR, FDA) and, compared to glass-filled polyamides, offers a specific weight that is approx. 15% lower, which results in reduced volume costs. The flame-retardant effect of the nanoparticles improves the fire behavior.

ZELLAMID 202 XN ist die Alternative für viele Anwendungen, bei denen andere Produkte die notwendigen Eigenschaften (z.B. erhöhte Gebrauchstemperatur) nicht aufweisen, da Standardmaterialien oft zu weich, wie z.B. PTFE oder zu kostspielig wie PEEK sind. Im Vergleich zu glasgefüllten Polyamiden ist dieses Material leichter zu bearbeiten, da kein Vorwärmen oder die Verwendung von Diamant-Werkzeug notwendig ist.ZELLAMID 202 XN is the alternative for many applications in which other products do not have the necessary properties (e.g. increased service temperature), as standard materials are often too soft, e.g. PTFE or too expensive like PEEK. Compared to glass-filled polyamides, this material is easier to machine because no preheating or the use of diamond tools is necessary.

VESTAKEEP® PEEK Typen für die Medizintechnik (Evonik Industries AG, Essen, Deutschland):
Für Anwendungen in der Medizintechnik sind die Produkte VESTAKEEP® M2G, VESTAKEEP® 12G, VESTAKEEP® M4G, VESTAKEEP® 14G, und das Pulver VESTAKEEP® M4P erhältlich. Die Rezeptur dieser Produkte ist auf eine hohe Biokompatibilität abgestimmt und eine Chargenprüfung "in vitro" auf Zytotoxizität nach EN ISO 10993-5 bietet zusätzliche Sicherheit.VESTAKEEP® PEEK grades for medical technology (Evonik Industries AG, Essen, Germany):
The products VESTAKEEP® M2G, VESTAKEEP® 12G, VESTAKEEP® M4G, VESTAKEEP® 14G, and the powder VESTAKEEP® M4P are available for applications in medical technology. The formulation of these products is tailored to a high level of biocompatibility and an "in vitro" batch test for cytotoxicity according to EN ISO 10993-5 offers additional security.

Claims (12)

  1. Method for the production of an adhesive bond between (a) the surface of dental frameworks produced on the basis of high-performance polymers comprising polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyoxymethylene (POM) or polyamides, and (b) dental composites, by
    A creating retentive anchorings by means of mechanical pre-treatment of the surface of the respective framework;
    B applying a low viscous or flowable, solvent-free adhesive agent containing a monomer mixture of polymethyl methacrylate, methyl methacrylate, at least one bifunctional methacrylate-based cross-linking monomer, initiator(s), and optionally stabiliser(s) and other additives, including
    (i) wetting of the surface,
    (ii) penetration into existing cavities, and
    (iii) formation of a dispersion layer or a film having a layer thickness of 0.5 to 2.5 µm, for single application, and of 4.5 to 7.5 µm, for double application, of the adhesive agent;
    C curing the dispersion layer or the film of step B at least in part; and
    D applying a dental composite or an opaque onto the product of step C.
  2. Method according to claim 1, wherein the adhesive agent contains UDMA, MMA, PMMA, photoinitiator(s) and stabiliser(s).
  3. Method according to claim 2, wherein the PMMA is partially dissolved in MMA.
  4. Method according to any one of the preceding claims, wherein the adhesive agent contains an agent for adjusting the viscosity.
  5. Method according to any one of the preceding claims, wherein the adhesive agent contains fine precipitated silica or pyrogenic silica.
  6. Method according to any one of the preceding claims, wherein mechanical pre-treatment of the surface is carried out by sandblasting.
  7. Method according to any one of the preceding claims, wherein sandblasting is carried out with 110 µm corundum.
  8. Method according to any one of the preceding claims, wherein the adhesive agent has a viscosity of 10 - 30 mPa·s at 23 °C.
  9. Method according to any one of the preceding claims, wherein the adhesive agent additionally contains inorganic pigments.
  10. Method according to any one of the preceding claims, wherein the application in D is carried out in several layers.
  11. Method according to any one of the preceding claims, wherein no waiting time is observed between C and D.
  12. Non-therapeutic use of a solvent-free adhesive agent containing initiator(s), polymethyl methacrylate, methyl methacrylate monomers and bifunctional methacrylate-based cross-linking agents,
    for the production of an adhesive bond between (a) the surface of dental frameworks produced on the basis of high-performance polymers comprising polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyoxymethylene (POM) or polyamides, and (b) dental composites, the respective framework being provided with retentive anchorings by mechanical pre-treatment of the surface, and the layer thickness of the adhesive agent being from 0.5 to 2.5 µm, for single application, and from 4.5 to 7.5 µm, for double application.
EP13003271.7A 2012-08-21 2013-06-27 Use of a solvent-free adhesion promoter to create an adhesive bond between dental composites and the surface of dental frameworks made of high-performance polymers Active EP2700394B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102012016418.1A DE102012016418B4 (en) 2012-08-21 2012-08-21 Dental bonding agent for high performance polymers

Publications (3)

Publication Number Publication Date
EP2700394A2 EP2700394A2 (en) 2014-02-26
EP2700394A3 EP2700394A3 (en) 2016-10-05
EP2700394B1 true EP2700394B1 (en) 2020-09-09

Family

ID=48699518

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13003271.7A Active EP2700394B1 (en) 2012-08-21 2013-06-27 Use of a solvent-free adhesion promoter to create an adhesive bond between dental composites and the surface of dental frameworks made of high-performance polymers

Country Status (4)

Country Link
US (1) US9144533B2 (en)
EP (1) EP2700394B1 (en)
CN (1) CN103622833B (en)
DE (1) DE102012016418B4 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10285914B2 (en) 2014-07-04 2019-05-14 Tokuyama Dental Corporation Bonding method, bonding kit, and bonding material
WO2018201242A1 (en) * 2017-05-01 2018-11-08 Dentalusis Technologie Dentaire Inc. Dual portion tooth restoration matrix
WO2020218446A1 (en) * 2019-04-24 2020-10-29 クラレノリタケデンタル株式会社 Curable composition for dental restoration
IT201900017585A1 (en) * 2019-09-30 2021-03-30 Luigi Salvatore Sposato New dental prosthesis in peek and three-layer composite resin.
EP4037602A1 (en) * 2019-09-30 2022-08-10 Luigi Salvatore Sposato A three-layer dental prosthesis
IT202000022735A1 (en) 2020-09-25 2022-03-25 Luigi Salvatore Sposato THREE-LAYER DENTAL PROSTHESIS
CN110628364A (en) * 2019-10-15 2019-12-31 常州先导智能科技有限公司 Digital photo-polymerization acrylic glue and preparation method thereof

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2174007B (en) * 1985-03-29 1989-09-06 Molten Corp Denture base provided with rubber-like resilient lining layer and process for producing the same.
DE3703080A1 (en) 1986-07-25 1988-01-28 Bayer Ag (METH) ACRYLIC ACID ESTER
DE3703120A1 (en) 1986-07-25 1988-01-28 Bayer Ag URETHANE GROUPS CONTAINING (METH) ACRYLIC ACID DERIVATIVES FROM TRICYCLO (5.2.1.0 (UP ARROW) 2 (UP ARROW) (UP ARROW). (UP ARROW) (UP ARROW) 6 (UP ARROW)) DECANES
JP2517753B2 (en) * 1988-12-28 1996-07-24 株式会社ジーシーデンタルプロダクツ Artificial tooth and its manufacturing method
JP2780722B2 (en) * 1989-10-02 1998-07-30 三井化学株式会社 Acrylic copolymer, its production method and its use
DE4233886C1 (en) * 1992-10-08 1994-03-31 Heraeus Kulzer Gmbh Conditioning agents and methods for pretreatment of plastic surfaces and use of the conditioning agent
US6121344A (en) * 1998-06-19 2000-09-19 Kerr Corporation Optimum particle sized hybrid composite
DE10043174A1 (en) * 2000-09-01 2002-03-21 Georg Barts Procedure for applying dental jewelry and set for performing the procedure
WO2002062901A1 (en) * 2001-02-06 2002-08-15 Pekka Vallittu Dental and medical polymer composites and compositions
DE10135529B4 (en) * 2001-07-20 2005-09-08 Forschungszentrum Karlsruhe Gmbh Adhesive, its use and method of bonding two objects
US7081485B2 (en) * 2002-08-21 2006-07-25 Bisco, Inc. Non-volatile dental compositions containing multifunctional acrylate compounds and lacking an oxygen-inhibited layer
US7214262B2 (en) * 2004-09-23 2007-05-08 I Did It, Inc. Temporary cosmetic dental surface coating
US20060166159A1 (en) * 2005-01-25 2006-07-27 Norbert Abels Laser shaping of green metal body used in manufacturing an orthodontic bracket
WO2007088628A1 (en) * 2006-02-03 2007-08-09 Kabushiki Kaisha Shofu Composite resin cement for dental use, primer for dental use and adhesive kit for dental use containing the same
DE102006050153A1 (en) * 2006-10-25 2008-05-08 Ivoclar Vivadent Ag Microencapsulated photoinitiators and their use for dental materials
DE102007013285A1 (en) 2007-03-16 2008-09-18 S&C Polymer Silicon- und Composite Spezialitäten GmbH Conditioning agent and method for bonding curable mixtures of molded articles made of filled high-temperature resistant plastics
US7658193B2 (en) * 2007-06-04 2010-02-09 Hayloft Enterprises, Inc. Interocclusal appliance and method
DE102007034457A1 (en) * 2007-07-20 2009-01-22 Heraeus Kulzer Gmbh Dental composites with low shrinkage stress and high flexural strength
RU2472708C2 (en) * 2008-10-15 2013-01-20 Зм Инновейтив Пропертиз Компани Filler and composite materials with zirconium and silica nanoparticles
DE102011003289A1 (en) * 2011-01-27 2012-08-02 Voco Gmbh Dental provisional superstructures as well as materials for their production and corresponding methods
US20130017511A1 (en) * 2011-07-15 2013-01-17 Shofu, Inc. Implant fixture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
DE102012016418A9 (en) 2015-04-16
EP2700394A2 (en) 2014-02-26
CN103622833A (en) 2014-03-12
US9144533B2 (en) 2015-09-29
DE102012016418A1 (en) 2014-02-27
CN103622833B (en) 2016-09-28
DE102012016418B4 (en) 2024-04-25
EP2700394A3 (en) 2016-10-05
US20140053965A1 (en) 2014-02-27

Similar Documents

Publication Publication Date Title
EP2700394B1 (en) Use of a solvent-free adhesion promoter to create an adhesive bond between dental composites and the surface of dental frameworks made of high-performance polymers
Miragaya et al. Evaluation of self-adhesive resin cement bond strength to yttria-stabilized zirconia ceramic (Y-TZP) using four surface treatments
DE4029230C2 (en) Polymerizable dental material
Yadav et al. Biomaterials for dental composite applications: A comprehensive review of physical, chemical, mechanical, thermal, tribological, and biological properties
EP3760181B1 (en) Dental composite block for preparing permanent indirect restorations in cad/cam method
EP0802221B1 (en) Silica based filler, process for its production and use thereof
EP3375407B1 (en) Grinding blank for producing an indirect dental restoration, corresponding uses and method
WO1999037272A1 (en) Rebase material for prosthesis and method for the production thereof
EP1862187B1 (en) Bone cement with improved mechanical properties and method for its manufacture
EP2153812A1 (en) X-ray opaque infiltrant
EP1945178B1 (en) Method for producing composites that can be used in dentistry
DE102007013285A1 (en) Conditioning agent and method for bonding curable mixtures of molded articles made of filled high-temperature resistant plastics
EP1360245B1 (en) Adhesives for metal-polymer composites
DE4000302C1 (en)
DD293486A5 (en) DENTAL RESTORATION MATERIALS
EP2346539B1 (en) Polymerizable multi-component prosthesis starting material, particularly for dental prostheses
DE10253481B4 (en) Composite material and use of a composite material
EP0434010B1 (en) Adhesion promoting composition (blend) for dental prosthetics and its use as dental adhesive
WO2013167484A2 (en) Use of an unfilled or filler-filled, organically modified silica (hetero)polycondensate in medical and non-medical processes for modifying the surface of a body made of a previously hardened, unfilled or filler-filled silica (hetero)polycondensate, more particularly for "chairside" treatment in dentistry
DE112014003310T5 (en) Infiltrant for dental ceramics
Veronesi et al. Sviluppo e caratterizzazione di materiali nano-rinforzati per applicazioni odontoiatriche
DD293487A5 (en) dental composites
EP2422824A2 (en) Basic prosthesis material, in particular for dental prosthetics
DE69835507T3 (en) DENTAL MATERIALS WITH FILLERS IN THE NANO AREA

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130704

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIC1 Information provided on ipc code assigned before grant

Ipc: A61K 6/00 20060101AFI20160829BHEP

Ipc: A61K 6/083 20060101ALI20160829BHEP

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: KULZER GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180702

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 502013015099

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: A61K0006000000

Ipc: A61K0006300000

RIC1 Information provided on ipc code assigned before grant

Ipc: A61K 6/887 20200101ALI20200207BHEP

Ipc: A61K 6/30 20200101AFI20200207BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200320

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

INTC Intention to grant announced (deleted)
GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

INTG Intention to grant announced

Effective date: 20200805

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1310662

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200915

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013015099

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: DENNEMEYER AG, CH

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201210

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201209

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201209

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200909

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210111

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210109

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013015099

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20210610

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210630

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1310662

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220914

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230623

Year of fee payment: 11

Ref country code: GB

Payment date: 20230622

Year of fee payment: 11

Ref country code: CH

Payment date: 20230702

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200909